EP1176219A1 - Legierung zum wasserstoffspeichern, verfahren zum absorbieren und freisetzen von wasserstoff durch den gebrauch der legierung und wasserstoffbrennstoffzelle zur anwendung des verfahrens - Google Patents

Legierung zum wasserstoffspeichern, verfahren zum absorbieren und freisetzen von wasserstoff durch den gebrauch der legierung und wasserstoffbrennstoffzelle zur anwendung des verfahrens Download PDF

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Publication number
EP1176219A1
EP1176219A1 EP99973803A EP99973803A EP1176219A1 EP 1176219 A1 EP1176219 A1 EP 1176219A1 EP 99973803 A EP99973803 A EP 99973803A EP 99973803 A EP99973803 A EP 99973803A EP 1176219 A1 EP1176219 A1 EP 1176219A1
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Prior art keywords
hydrogen
alloy
temperature
hydrogen storage
metal alloy
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French (fr)
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EP1176219A4 (de
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Masuo Okada
Takahiro Kuriiwa
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OKADA, MASUO
Dowa Holdings Co Ltd
Tohoku Techno Arch Co Ltd
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Tohoku Techno Arch Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • C22C27/025—Alloys based on vanadium, niobium, or tantalum alloys based on vanadium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S420/00—Alloys or metallic compositions
    • Y10S420/90—Hydrogen storage

Definitions

  • the present invention relates to a method for absorption and release of hydrogen where a hydrogen storage metal alloy is repeatedly subjected to pressurization and depressurization of hydrogen.
  • the present invention relates to a hydrogen storage metal alloy having a two-stage plateau- or inclined plateau-property.
  • the present invention relates to a method for absorption and release of hydrogen where the amount of released hydrogen increases within practical pressure ranges and temperature ranges, to a hydrogen storage metal alloy suitable for such a method for absorption and release of hydrogen and to a hydrogen fuel battery using the above method for absorption and release of hydrogen.
  • hydrogen storage metal alloys are metals/alloys which can absorb and release the hydrogen under an appropriate condition and, by the use of such alloys, it is possible to store the hydrogen not only at lower pressure but also at higher density as compared to the case of the conventional hydrogen cylinders.
  • the hydrogen volume density thereof is nearly equal to or rather greater than that of liquid or solid hydrogen.
  • These hydrogen storage metal alloys which have been chiefly investigated are, for example, those alloys which each have a body-centered cubic (hereinafter, referred to as "BCC") structure, including V, Nb, Ta or Cr-Ti-Mn alloys, Cr-Ti-V alloys, etc. as proposed in Japanese Unexamined Patent Publication(Kokai)No. 10-110225 (JP, A, 10-110225). It has been known that those alloys adsorb and store hydrogen in greater quantities as compared with AB5 alloys such as LaNi5 and AB2 alloys such as TiMn2 which have been practically used until now.
  • BCC body-centered cubic
  • V reacts with hydrogen at ambient temperature and forms two kinds of hydrides depending upon the pressure of hydrogen.
  • a very stable hydride is formed as V ⁇ VH 0.8 ( ⁇ phase ⁇ ⁇ phase) (hereinafter, referred to as " low-pressure plateau part") and, at around room temperature, a reverse reaction thereof rarely happens.
  • VH 0.8 ⁇ VH 2.01 ( ⁇ phase ⁇ ⁇ phase; referred to as "high-pressure plateau part").
  • the equilibrium hydrogen pressure of this reaction is appropriate (approximately a few atmospheric pressure at around room temperature). Therefore, such V-containing BCC alloys have been briskly studied as high-capacity hydrogen storage metal alloys.
  • FIG. 1 is a conceptional chart of a PCT curve of a single substance V having a two-stage plateau comprised of the aforementioned low-plateau and high-plateau parts.
  • the flat region at the hydrogen pressure of 10 -1 Pa in FIG. 1 is a low-pressure plateau part and the flat region at the hydrogen pressure of 10 6 Pa is a high-pressure plateau part.
  • the inclined region between the low-pressure plateau part and the high-pressure plateau part is a region complying with Sieverts's law.
  • an example of the metal having such a two-stage plateau is Nb (low-pressure phase: NbH, high-pressure phase: NbH2).
  • Ti shows a two-stage plateau by a transformation of ⁇ ⁇ ⁇ ⁇ ⁇ although it operates at elevated temperature.
  • An intermetallic compound having a two-stageplateauin cludes FeTi which works at near 40°C.
  • alloys such as (Zr, Ti)V 2 show an inclined plateau and those alloys are also used as hydrogen storage metal alloys.
  • JP, A, 10-110225 and JP, A, 07-252560 both which disclose the methods where hydrogen is absorbed and released at a constant temperature, provided that, in the latter JP, A, 07-252560, the activating pretreatment is carried out by means of a two-stage treatment comprising a low temperature in the former stage and a high temperature in the latter stage while the temperature for hydrogen absorption and desorption is constant (20°C).
  • JP, A, 10-110225 and JP, A, 07-252560 both which disclose the methods where hydrogen is absorbed and released at a constant temperature, provided that, in the latter JP, A, 07-252560, the activating pretreatment is carried out by means of a two-stage treatment comprising a low temperature in the former stage and a high temperature in the latter stage while the temperature for hydrogen absorption and desorption is constant (20°C).
  • the hydrogen in the reaction of ⁇ phase ⁇ ⁇ phase i.e., the reaction at the low-pressure plateau part (for example, the reaction of V ⁇ VH 0.8 in the case of V) contributes to the reaction of absorption and desorption in addition to the ⁇ -phase region of the BCC type alloy (a portion complying with a Sieverts's law between a low-pressure plateau region and a high-pressure plateau region).
  • the reaction at the low-pressure plateau part for example, the reaction of V ⁇ VH 0.8 in the case of V
  • an object of the present invention is, with regard to the conventional pure V or pure Nb showing a two-stage plateau or inclined plateau region or BCC solid solution alloys including not only solid solutions showing a hydrogen absorption/desorption reaction similar to the above-mentioned metal, but also Ti-Cr system alloys, etc., to provide a hydrogen storage metal alloy in which the hydrogen not only between ⁇ phase ⁇ ⁇ phase, i.e.
  • the present invention provides a novel hydrogen storage metal alloy.
  • the novel hydrogen storage metal alloy has the following characteristics:
  • the occluded hydrogen can be unstabilized in the alloy so that the alloy temperature may be brought to high (T2) during the hydrogen desorption process, thereby facilitating the release of hydrogen during the aforementioned low-pressure plateau region or the lower plateau region of the inclined plateau region, and therefore the occluded hydrogen at the low-pressure plateau region or the lower plateau region of the inclined plateau region, which has been neither desorbed nor utilized at all, can be taken out as utilizable hydrogen, with the result that the amount of the utilizable hydrogen in such a hydrogen storage metal alloy will be increased.
  • the hydrogen storage metal alloys of the present invention are those wherein the alloy temperature (T1) during the hydrogen-absorbing process may range from the extremely low temperature in the living areas on the earth to 373K.
  • the alloy temperature (T1) during the hydrogen-absorbing process can be made near an ambient temperature region whereby the practicability can be improved.
  • the hydrogen storage metal alloys of the present invention are V alloys which each not only have a suitably adjusted composition to reduce the stability of the occluded hydrogen as aforementioned but also contain 0 to 95 at% of at least one or more members selected from the group consisting of Nb, Ta, W, Mo, Ti, Cr, Mn, Fe, Al, B, Co, Cu, Ge, Ni and Si.
  • the alloys each having such a composition are highly effective in unstabilizing the occluded hydrogen therein and therefore suitable for releasing a large amount of hydrogen therefrom during the low-pressure plateau region or the lower plateau region of the inclined plateau by raising the alloy temperature during a hydrogen-desorbing process.
  • the hydrogen storage metal alloys of the present invention are those alloys which each have not only a suitably adjusted composition to reduce the stability of the occluded hydrogen as aforementioned but also a fundamental composition of the formula: V a Ti (41-0.4a+b) Cr (59-0.6a-b) wherein 0 ⁇ a ⁇ 70 at% and -10 ⁇ b ⁇ 10 at%.
  • the alloys each having such a composition can occlude a large amount of hydrogen at the high-pressure plateau region and are greatly effective in unstabilizing the occluded hydrogen therein. Therefore, such alloys are preferable to release a large quantity of occluded hydrogen during the low-pressure plateau region or the lower plateau region of the inclined plateau by raising the alloy temperature during the hydrogen-desorbing process and have an effective amount of utilizable hydrogen in great quantities, thereby giving a high practicability.
  • the hydrogen storage metal alloys of the present invention are those alloys which each have not only a suitably adjusted composition to reduce the stability of the occluded hydrogen as aforementioned but also a fundamental composition of the formula: V (a-d) M2 d Ti (41-0.4a+b) Cr (59-0.6a-b-c) M c wherein 0 ⁇ a ⁇ 70 at%, -10 ⁇ b ⁇ 10 + c, 0 ⁇ c, 0 ⁇ d ⁇ a, M is at least one or more members selected from the group consisting of Nb, Mo, Ta, W, Mn, Fe, Al, B, C, Co, Cu, Ge, Ln (various lanthanoid metals), N, Ni, P and Si, and M2 is at least one or more members selected from the group consisting of Mo, Nb, Ta, W, Mn, Fe and Al.
  • the alloys each having such a composition can occlude a large amount of hydrogen at the high-pressure plateau region and are greatly effective in unstabilizing the occluded hydrogen therein. Therefore, such alloys are preferable to release a large quantity of occluded hydrogen during the low-pressure plateau region or the lower plateau region of the inclined plateau by raising the alloy temperature during the hydrogen-desorbing process and have an effective amount of utilizable hydrogen in great quantities, thereby giving a high practicability.
  • the hydrogen storage metal alloys according to the present invention are those wherein the tissue structure of the above-mentioned suitably adjusted hydrogen storage metal alloy is of a body-centered cubic structure mono phase without any spinodal decomposition phase or has a body-centered cubic structure together with only a minimum spinodal decomposition phase which is unavoidably produced.
  • the hydrogen storage metal alloy has a minimum spinodal decomposition phase or has no spinodal decomposition phase, thereby enabling a decrease in hydrogen adsorption capacity due to the formation of spinodal decomposition phase to be suppressed as little as possible.
  • a method for absorbing and releasing hydrogen by using the hydrogen storage metal alloy according to the present invention comprises:
  • the alloy temperature (T1) during the above hydrogen-absorbing process is within a range of from the extremely low temperature in the living areas on the earth to 373K in the method for absorbing and releasing hydrogen by using the hydrogen storage metal alloy according to the present invention.
  • the alloy temperature (T1) during the hydrogen-absorbing process can be made near an ambient temperature region whereby the practicability can be improved.
  • the method for absorbing and releasing hydrogen according to the present invention comprises using a hydrogen storage metal alloy wherein the composition ratio of the constituent metals for the alloy is adjusted to an appropriate range in order to reduce the stability of the hydrogen occluded in the alloy during either the low-pressure plateau region or the lower plateau region of the inclined plateau such that the temperature of the said alloy can be brought to the above high temperature (T2) whereby at least part of the occluded hydrogen will be made desorbable during either the low-pressure plateau region in the above-mentioned two-stage plateau or the lower plateau region of the inclined plateau.
  • T2 high temperature
  • the occluded hydrogen can be unstabilized in the alloy, thereby facilitating the release of hydrogen from either the above low-pressure plateau region or the lower plateau region of the inclined plateau when the temperature of the said alloy is made higher (T2) during the hydrogen release process, with the result that the amount of effective hydrogen can be increased.
  • the method for absorbing and releasing hydrogen according to the present invention comprises using a hydrogen storage metal alloy wherein the aforementioned adjustment is in such a manner that the composition ratio of the constituent metals for the alloy is adjusted suitably so as to reduce the stability of the occluded hydrogen in the alloy within either the low-pressure plateau region or the lower plateau region of the inclined plateau.
  • the method for absorbing and releasing hydrogen according to the present invention comprises using a hydrogen storage metal alloy with a suitably adjusted composition to reduce the stability of the above occluded hydrogen, said hydrogen storage metal alloy being a v alloy containing 0 to 95 at% of at least one or more members selected from the group consisting of Nb, Ta, W, Mo, Ti, Cr, Mn, Fe, Al, B, Co, Cu, Ge, Ni and Si.
  • the alloy having such a composition is highly effective in unstabilizing the occluded hydrogen therein and therefore suitable for releasing a great deal of hydrogen from the low-pressure plateau region or the lower plateau region of the inclined plateau by raising the alloy temperature during the hydrogen release process.
  • the method for absorbing and releasing hydrogen according to the present invention comprises using a hydrogen storage metal alloy with a suitably adjusted composition to reduce the stability of the above occluded hydrogen, said hydrogen storage metal alloy having a fundamental composition of the formula: V a Ti (41-0.4a+b) Cr (59-0.6a-b) wherein 0 ⁇ a ⁇ 70 at% and -10 ⁇ b ⁇ 10 at%.
  • the alloy having such a composition has not only a great deal of occluded hydrogen therein at the high-pressure plateau region but also a high activity in unstabilizing the hydrogen occluded in the alloy. Therefore, such alloys are suitable for releasing a great deal of hydrogen from the low-pressure plateau region or the lower plateau region of inclined plateau by raising the alloy temperature during the hydrogen release process and highly practicable because a great amount of effective hydrogen is utilizable therein.
  • the method for absorbing and releasing hydrogen according to the present invention comprises using a hydrogen storage metal alloy with a suitably adjusted composition to reduce the stability of the above occluded hydrogen, said hydrogen storage metal alloy having a fundamental composition of the formula: V (a+b) M2 d Ti (41-0.4a+b) M c wherein 0 ⁇ a ⁇ 70 at%, -10 ⁇ b ⁇ 10 + c, 0 ⁇ c, 0 ⁇ d ⁇ a, M is at least one or more members selected from the group consisting of Nb, Mo, Ta, W, Mn, Fe, Al, B, C, Co, Cu, Ge, Ln (various lanthanoid metals), N, Ni, P and Si, and M2 is at least one or more members selected from the group consisting of Mo, Nb, Ta, W, Fe and Al.
  • the alloy having such a composition has not only a great deal of occluded hydrogen at the high-pressure plateau region but also a high activity in unstabilizing the hydrogen occluded in the alloy. Therefore, such alloys are suitable for releasing a great deal of hydrogen from the low-pressure plateau region or the lower plateau region of inclined plateau by raising the alloy temperature during the hydrogen release process and highly practicable because a great amount of effective hydrogen is utilizable therein.
  • the suitable admixture with at least one or more elements selected from the group consisting of the above-mentioned lanthanoid metals, N, Ni, P and Si leads to a decrease in the melting point of the alloy and an improvement in the flatness of the plateau resulted thereby whereupon the resultant alloy products are successful in suppressing a decrease in hydrogen adsorption capacity because a heating treatment which is apt to cause a spinodal decomposition is not applied or a treating time is shortened.
  • the method for absorbing and releasing hydrogen according to the present invention comprises using a hydrogen storage metal alloy wherein the tissue structure of the aforementioned suitably adjusted hydrogen storage metal alloy is of a body-centered cubic structure mono phase without any spinodal decomposition phase or has a body-centered cubic structure together with only a minimum spinodal decomposition phase which is unavoidably produced.
  • the hydrogen storage metal alloy has a minimum spinodal decomposition phase or has no spinodal decomposition phase. Therefore, a reduction in the amount of occluded hydrogen by the formation of spinodal decomposition phase can be suppressed as little as possible.
  • the hydrogen fuel battery of the present invention is characterized in that the battery is equipped with
  • the temperature (T2) of the aforementioned hydrogen storage metal alloy can be made higher than the temperature (T1) during the hydrogen-absorbing process whereby it is now possible to take out as a utilizable hydrogen the occluded hydrogen at the low-pressure plateau region or at the lower plateau region of the inclined plateau, said occluded hydrogen which has been neither desorbed from the hydrogen storage metal alloy nor utilized before, and to increase electric energy obtained by the fuel battery cell.
  • the aforementioned controller is capable of appropriately controlling a pressure, temperature and flow rate of the hydrogen gas supplied from the above-mentioned hydrogen storage tank to the above-mentioned fuel battery cell.
  • the pressure, temperature and flow rate of hydrogen gas can be controlled whereby it is possible to control amounts of generated electric energy in the fuel battery cell appropriately depending upon the load and to enhance the utilizing efficiency of the hydrogen used in the said fuel battery cell.
  • the above-mentioned temperature controlling means is arranged so as to enable the heat discharged from the above-mentioned fuel battery cell or the exhaust gas discharged from the said fuel battery cell to be utilized for the above-mentioned heating.
  • the discharged heat or the exhausted heat of the fuel battery cell can be utilized for raising the temperature of the above-mentioned hydrogen storage metal alloy whereby no electric energy or the like is necessary for raising the temperature of such a hydrogen storage metal alloy and the efficiency throughout the hydrogen fuel battery can be enhanced.
  • FIG. 1 is a conceptional diagram of a PCT curve of metal V.
  • FIG. 2 is a graph showing a typical relation between a hydrogen absorption-dissociation curve and temperature in LaNis, etc.
  • FIG. 3 is a graph showing amounts of released hydrogen depending on the rise in the temperature upon hydrogen release in LaNi5, etc.
  • FIG. 4 is a graph showing a hydrogen absorption characteristic (313 K) of V x -Ti (40-0.4x) -Cr (60-0.6x) cast alloy.
  • FIG. 5 is a graph showing a hydrogen absorption characteristic under the ordinary cycle in a heat-treated V x -Ti 37.5 -Cr (62.5-x) alloy.
  • FIG. 6 is a graph showing an influence of the measuring temperature on a hydrogen absorption characteristic in a V 70 Zr 0.5 Ti 11.5 cr 18 alloy.
  • FIG. 7 is a graph showing a hydrogen absorption and desorption characteristic when the measuring temperature is 303K and 323K in a V 70 Zr 0.5 Ti 11.5 Cr 18 alloy.
  • FIG. 8 is a graph (conceptional diagram) showing an influence of the temperature difference in a PCT curve having a two-stage plateau.
  • FIG. 9 is a graph (conceptional diagram) showing a volume increase of the temperature difference in a PCT curve having a two-stage plateau.
  • FIG. 10 is a graph showing the hydrogen absorption-desorption characteristic obtained by conducting an ordinary absorption-desorption cycle (the second cycle) and a cycle according to the method of the present invention (the third cycle) for a V 40 Ti 25 Cr 35 alloy.
  • FIG. 11 is a graph showing a hydrogen absorption-desorption characteristic when the measuring temperature is 313K in a V 30 Ti 30 Cr 40 alloy.
  • FIG. 12 is a graph showing a hydrogen absorption-desorption characteristic obtained by conducting the fourth and the fifth cycles after the absorption-desorption cycle conducted in FIG. 11.
  • FIG. 13 is a graph showing a hydrogen absorption characteristic in the third cycle of a V 35 Ti 25 Cr 40 alloy subjected to a heating treatment at 1573K for a given time.
  • FIG. 15 is a graph showing a hydrogen absorption characteristic at 313K of a V 27.5 Ti 30 Cr 42.5 alloy.
  • FIG. 16 is a graph showing an effective hydrogen absorption characteristic when the method of the present invention is applied to a V 27.5 Ti 30 Cr 42.5 alloy.
  • FIG. 17 is a graph showing a conceptional proof (upon hydrogen release; raised from 313K to 368K, and dissociation pressure controlled) of the differential temperature method using a V 20 Ti 35 Cr 45 sample.
  • FIG. 18 is a graph showing a hydrogen absorption characteristic when the alloy working method of the present invention is applied to a V x -Ti (40-0.4x) -Cr (60-0.6x) cast alloy which is an alloy according to the present invention.
  • FIG. 19 is a hydrogen absorption characteristic graph showing an influence of a temperature rise on dissociation pressure in a V 40 Nb 3 Ti 25 Cr 32 alloy.
  • FIG. 20 is a graph showing a hydrogen absorption characteristic when the differential temperature method of the present invention is applied to a heat-treated V x -Ti 37.5 -Cr (62. 5-x) alloy.
  • FIG. 21 is a system flow chart showing an embodiment of the hydrogen fuel battery according to the present invention.
  • FIG. 22 is a schematic chart showing a mechanism of generation of electric power in the fuel battery cell used in the hydrogen fuel battery of the present invention.
  • the reason why the composition of the alloy according to the present invention is defined as above is that a reaction of V ⁇ VH 0.8 ( ⁇ phase) in pure V is very stable and it is difficult to dissociate hydrogen from VH 0.8 under a practical condition but, when it is kept in vacuo at 673K (300°C ) for example, it is possible to dehydrogenate it.
  • V(M)H 0.8 V(M)H 0.8
  • the alloy of the present invention is in a composition where a spinodal decomposition is apt to take place, it is concluded to be allowed within an extent of being unavoidably formed because, as will be mentioned later in detail, a spinodal decomposition tissue is a source of deterioration of a hydrogen absorption characteristic.
  • V is capable of forming a BCC mono phase within a composition range of 5 to 100 at%.
  • Ti and Cr are the elements which lower the stability of VH 0.8 when made into an alloy with V.
  • the atomic radius of Ti (1.47 ⁇ ) is bigger than that of V (1.34 ⁇ ) and that of Cr (1.30 ⁇ ). Therefore, when V is substituted with Ti and Cr and an amount of substituent Ti is more than that of substituent Cr, a lattice constant of the BCC main phase becomes big whereby a plateau pressure of a PCT curve lowers .
  • V is greatly substituted with Ti and Cr so as to lessen the stability of V(M)H 0.8 formed at the above-mentioned lower pressure plateau is lowered, thereby aiming at increasing an amount of released hydrogen from the said alloy.
  • the hydrogen dissociation pressure at the high-pressure plateau region is to be kept within a practical range and, for such a purpose, the substitution ratio of Ti and Cr in the substitution with Ti and Cr as mentioned above comes to an important factor.
  • the starting composition in the present invention is V 70 Ti 12 Cr 18 (figures are in atomic %).
  • an alloy of Ti 40 Cr 60 was produced.
  • FIG. 4 shows a hydrogen absorption characteristic of a V x -Ti (40-0.4x) -Cr (60-0.6x) cast alloy at 313 K (40°C). It is understood that the alloy wherein the level of V has been made less than 80 at% shows a good characteristic.
  • the term b is set to give an extent for the selection of alloy components so as to enable the dissociation pressure to be adjusted to some extent and -10 ⁇ b ⁇ 10 at% is basic.
  • the basic formula is V a Ti (41-0.4a+b) Cr (59-0.5a-b-c) M c .
  • a condition for b is introduced to be -10 ⁇ b ⁇ 10+c-at%.
  • This alloy may also be subjected to a hydrogen absorption/desorption at a predetermined temperature like in the conventional case. Although only about one-half of theoretical amount of hydrogen can be taken out in the case of the conventional alloys, there is an advantage in the alloy of the present invention that a great increase in hydrogen desorption capacity is achieved.
  • the BCC type V-Ti-Cr system alloy containing a micro amount of V has a high hydrogen storage capacity.
  • the element which is apt to form a BCC structure with Ti and Cr, like V, is Mo, Nb, Ta, W, Fe or Al.
  • an M2 term the component capable of accelerating the BCC formation
  • an amount of the substituent M2 is defined as d-at% (0 ⁇ d ⁇ a) wherein the M2 component may also be utilized as the above-mentioned substituent term for Cr, i.e., the M term.
  • the hydrogen storage metal alloy according to the present invention provided as such is characterized in that the alloy is a hydrogen storage V type metal alloy having a two-stage plateau characteristic, and has a composition of the following formula: V (a-d) M2 d Ti (41-0.4a+b) Cr (59-0.6a-b-c) M c wherein 0 ⁇ a ⁇ 70 at%, -10 ⁇ b ⁇ 10 + c, 0 ⁇ c, 0 ⁇ d ⁇ a, M is at least one or more elements selected from the group consisting of Nb, Mo, Ta, W, Mn, Fe, Al, B, C, Co, Cu, Ge, Ln (various lanthanoid metals), N, Ni, P and Si, and M2 is at least one or more elements selected from the group consisting of Mo, Nb, Ta, W, Mn, Fe and Al, and the main phase of the alloy is in a body-centered cubic structure and do not have a spinodal decomposition tissue or has
  • the method of the present invention is a method for effectively utilizing the occluded hydrogen in a low-pressure plateau region of hydrogen storage metal alloy showing a two-stage plateau or inclined plateau characteristic which comprises:
  • the lowest limit in the above low-temperature region (T1) is an extremely low temperature in a living area where hydrogen can be utilized as an energy source and, at present, 243K is an example of such an extremely low temperature.
  • the above elevated temperature region (T2) is a temperature which is higher than the above low-temperature region (T1) which is the hydrogen-absorbing temperature.
  • the above elevated temperature region (T2) can be achieved by the use of a waste heat (usually about 70 to 100°C) generated at the fuel battery member upon operation (i.e., corresponding to the hydrogen release process) or a heat froma heater exclusively therefor when the hydrogen storage metal alloy is used, for example, as a tank for a fuel battery.
  • the method for absorbing and releasing hydrogen according to the present invention is applicable to various kinds of a body-centered cubic type hydrogen storage metal alloy, it is preferably applicable to Valloys, particularly, to hydrogen storage Vmetal alloys containing each 0 to 95 at% of at least one or more elements selected from the group consisting of Ti, Cr, Nb, Mo, Ta, W, Mn, Fe, Al, B, C, Co, Cu, Ge, Ln (various lanthanoid metals), N, Ni, P and Si.
  • the inventive effects of the method for absorbing and releasing hydrogen according to the present invention will be more specifically illustrated by citing the experiments conducted by the present inventors.
  • the alloys used as samples were prepared in such a manner that the materials were weighed so as to bring the weight of ingot to 14 g, arc-melted in an argon atmosphere of 40 kPa and dissolved and stirred repeatedly three times for enhancing the uniformity and the resulting cast ingots per se were used as samples or subjected to a heating treatment for homogenization at 1473K for 2 hours in an Ar atmosphere.
  • the hydrogen storage metal alloy having a two-stage plateau region does not show a clear decrease in amounts of absorbed and desorbed hydrogen even when operated at high temperature because the low-pressure plateau region or the inclined plateau region contributes to absorption and desorption of hydrogen when operation is carried out at high temperature as noted from the results as shown in FIG. 7, i.e., the hydrogen storage metal alloy begins to utilize a low-pressure plateau region.
  • FIG. 9 shows an increase in the hydrogen capacity.
  • a conceptional chart is shown in FIG. 9 which shows an increase in the hydrogen capacity.
  • FIG. 9 shows an increase in the hydrogen capacity.
  • the present inventors have found a possibility that an increase in amounts of released hydrogen can be achieved or a high capacity can be acquired for hydrogen storage metal alloy-equipped hydrogen tanks.
  • V 70 Zr 0.5 Ti 11.5 Cr 18 alloy of the present invention is capable of achieving an increase in the hydrogen release amount with elevating the temperature during the desorption stage, relying on a new principle different from the conventional V alloy.
  • the fact that such a conclusion can be applied to known V alloys having different compositions has been confirmed as follows:
  • the V 40 Ti 25 Cr 35 alloy which was reported in the aforementioned JP, A, 10-110225 (having a spinodal decomposition tissue as a result of a heat-treatment at 1473K for 2 hours) was subjected to an activating treatment followed by measurement for the first cycle and the second cycle at 313K (40°C), and further subjected to a deaeration at room temperature for 5 hours or more, and then at 368K (95°C) for 3 hours followed by measurement for the third cycle at 313K.
  • the PCT curves at the second cycle and the third cycle are shown in FIG. 9.
  • the amount of hydrogen which could be reversibly taken out therefrom was about 2.4 mass % which was in the same degree as that in the conventional report while in the third cycle wherein an elevated temperature process was introduced into the second cycle which was at the same low temperature as in the conventional case the amount of occluded hydrogen slightly increased to 2.49 mass %.
  • a V 30 Cr 30 Ti 40 alloy (having a spinodal decomposition tissue similarly to the alloy of FIG. 6) wherein the amount of V was further reduced as an alloy with an optimum composition to which the above cycle for effectively utilizing hydrogen was applicable was measured for PCT curve up to 3 cycles at the constant temperature of 313K. The results are shown in FIG. 1. The hydrogen storage amount obtained as a result thereof is in a similar degree with one reported already.
  • FIG. 13 shows a PCT absorption curve each of as cast and as heat-treated at 1573K for various retention time ranges V 35 Ti 25 Cr 40 alloys.
  • the results show that the hydrogen-absorption characteristic is better in the case where a heating treatment is not carried out at all or where the time for a heating treatment is as short as possible than the alloy which is fully in the form of a spinodal decomposition. Based upon such a finding, it is decided to permit the tissue of the alloys according to the present invention so far as it is in a BCC mono phase without any spinodal decomposition phase or with only a spinodal decomposition phase unavoidably produced.
  • the method of the present invention is applied to an alloy showing an inclined plateau whereby the low-temperature region can be effectively utilized for hydrogen absorption.
  • the results when the method of the present invention was applied to this sample are shown in FIG. 15.
  • the first cycle was carried out at the constant temperature in the same manner as in the conventional case, then a deaeration was carried out at 368K in each of the second and third cycles before measurement and the measurement was carried out at 313K whereup on the amount of occluded hydrogen increased up to 2.8 mass %.
  • the hydrogen can be utilized to the maximum extent.
  • the results are shown in FIG. 16.
  • the effectively utilized hydrogen amount is the difference between the hydrogen storage amount at 7 Mpa in the hydrogen-absorbing process at 313K and the residual hydrogen amount in the alloy at 0.01 MPa in the hydrogen release process at 368K. Accordingly, it is 2.7 mass %.
  • the curve shown by ⁇ is the case where hydrogen desorption was carried out at 368K and then hydrogen absorption was carried out at 313K showing a big storage amount. Accordingly, it is noted that the differential temperature method is effective.
  • the curve shown by ⁇ is the case where the operating temperature was elevated when the equilibrium dissociation pressure during the hydrogen release process arrived 0.05 MPa (temperature for each stage is mentioned in the drawing) and, as a result of heating, the dissociation pressure was controlled, the plateau region was flattened and the effective amount of hydrogen was greatly increased. It is noted from the drawing that the residual hydrogen amount in the alloy at 0.005 MPa is identical with that in the desorption curve ( ⁇ ) obtained at 368K.
  • FIG. 20 shows the results when the differential temperature method of the present invention was applied to a heat-treated V x -Ti 37-5 -Cr (62.5-x) alloy exerting the hydrogen storage amount of as high as 2.8 mass % (refer to FIG. 5). Even in the alloys where the level of V is brought to as small as 5 to 7.5 atom %, a hydrogen storage amount of about 3.0 mass % is achieved when the present invention is applied.
  • FIG. 5 absorption/desorption at the single temperature of 313K in the same fashion as in the conventional method
  • FIG. 21 is a system flow chart showing a preferred embodiment of the hydrogen fuel battery according to the present invention.
  • FIG. 22 is a schematic chart showing a mechanism of generation of electric power in the fuel battery cell used in the hydrogen fuel battery of the present invention.
  • the constitution of the hydrogen fuel battery in the above embodiment is as shown in FIG. 21.
  • the battery is mainly constituted from a hydrogen fuel tank (4) installed with a hydrogen storage metal alloy in which the composition of constituent elements is suitably adjusted so as to make the occluded hydrogen desorbable in the low-pressure plateau region by means of heating according to the present invention, said fuel tank (4) being capable of supplying the hydrogen occluded in the said hydrogen storage metal alloy to a fuel battery cell (1) which will be mentioned later;
  • the said controller (3) is connected to pumps (P1 to P5), electromagnetic valves (V1 to V11), pressure valves (B1, B2), a flowmeter (FM) and temperature sensors (TS1 to TS3) installed on various piping as shown by broken lines in FIG. 21.
  • LS in the drawing is a water level sensor in a storage tank in which water produced is stored upon cooling the steam discharged from the fuel battery cell (1) by a heat exchanger (5).
  • the hydrogen which is to be absorbed with the hydrogen storage metal alloy is supplied, as a starting material hydrogen (shown in FIG. 21), into the hydrogen fuel tank (4) by connecting a high-pressure hydrogen cylinder to a hydrogen supplying outlet followed by opening the valve (V1) whereupon the hydrogen storage metal alloy absorbs the hydrogen from the low-pressure plateau region to the high-pressure plateau region.
  • the above-mentioned controller (3) releases the valves (V9 and V10) connected to the heat exchanger (5) and also makes the pump (P5) in an operating state whereby the outer air is sent into the heat exchanger (5) to cool the above-mentioned cold/warm water with the outer air.
  • the hydrogen storage metal alloy is monitored for the temperature with the above-mentioned temperature sensor (TS3) and the circulation pump (P3) is appropriately operated so as to bring the temperature (T1) of the said hydrogen storage metal alloy to 40°C or lower whereby the above heat-exchanged cold/warm water is appropriately passed into the above-mentioned cooling/warming medium jacket to carry out the cooling of the hydrogen storage metal alloy.
  • the above-mentioned valve (V11) is closed and hydrogen absorption is finished.
  • the above-mentioned controller (3) opens the valve (V1), appropriately operates the above-mentioned pressure valve (B1) based upon the detection data from the flowmeter (FM), pressure sensor (PM) and temperature sensor (TS1) installed to the downstream of the pressure valve (B1) so as to adjust a pressure and flow rate of hydrogen to be supplied to the fuel battery cell (1) from the hydrogen fuel tank (4) to a predetermined pressure, and controls the temperature of hydrogen to be supplied with appropriately passing the above-mentioned cold/warm water through the above-mentioned cooling/warming medium jacket. Simultaneously, the controller (3)operatesthepump(P1) so that the oxygen in the outer air is sent into the above-mentioned fuel battery cell (1).
  • Each operation of the members including the controller (3) before generating electric power by the fuel battery cell can be carried out by means of a storage battery (not shown) installed in the said hydrogen fuel battery.
  • a storage battery not shown
  • direct current is obtained in the said fuel battery cell (1), as shown in FIG. 22, with the reaction which is reverse to the production of hydrogen and oxygen via electrolysis of water by application of direct current to water to which an electrolyte has been added. Therefore, hydrogen molecules supplied from the hydrogen fuel tank (4) become hydrogen ions by releasing electrons at a hydrogen electrode and the resulting electrons move to a positive electrode side whereupon electric power is generated.
  • Such hydrogen ions move to the positive electrode side in an electrolyte, receive electrons at the positive electrode to return to hydrogen atoms and simultaneously react with oxygen contained in the above-mentioned supplied outer air to form water (steam).
  • the said controller (3) opens the valves (V5, V7) (naturally, the valves V9, V10 and V6 are in a closed state) to introduce the exhaust gas into the heat exchanger (5) so that the heat would be exchanged.
  • the exhaust gas cooled by the said heat exchange is discharged to outer air via a storage tank while the water produced by the said cooling is stored in a storage tank.
  • the valves (V5 and V7) are in a closed state and, after the valve V6 is opened and the above-mentioned exhaust gas is exposed to air in the storage tank whereupon the steam is appropriately removed, it is discharged to outer air. It goes without saying that, during such an operation stage, the valve (V4) is in an opened state.
  • the hydrogen which is supplied from the above-mentioned hydrogen fuel tank (4) originates in the high-pressure plateau region of the above-mentioned hydrogen storage metal alloy and therefore the temperature of the hydrogen storage metal alloy is controlled to a temperature nearly equivalent to that during the above-mentioned hydrogen absorption.
  • the above-mentioned controller (3) conducts its valve control as mentioned above for the heat exchange in the heat exchanger (5) and simultaneously the cold/warm water heated by the heat exchanger is passed to the hydrogen fuel tank (4) by making the circulation pump (P3) in an operating state whereupon heating of the hydrogen storage metal alloy is started.
  • the temperature of the above-mentioned hydrogen storage metal alloy is elevated and as aforementioned the occluded hydrogen in the lower region of the inclined plateau or in the low-pressure plateau region is desorbed.
  • Such a desorbed hydrogen is supplied to the fuel battery cell (1) so that generation of electric power is continuously carried out whereupon the electric power generating capacity of the hydrogen fuel battery can be significantly improved.
  • T2 heating temperature of such a hydrogen storage metal alloy
  • water since water is used as a cooling/warming medium in this example, its upper limit is around 90°C but the present invention is not limited to.
  • a hydrogen storage metal alloy may be heated with a heater or the like to bring it to a higher temperature.
  • temperature upon hydrogen absorption is made not higher than 40°C which is practical by means of cooling due to heat release with a heat exchange to the outer air but the present invention is not limited to.
  • Such a cooling may be carried out by installment of a cooling apparatus or by using as the cooling/warming medium a cooling medium such as flon or ammonia together with a heat pump in which a heat exchange is carried out by compression and expansion of such a cooling medium.
  • a heat pump it is also possible to carry out both cooling and heating by the use of a Peltier element.
  • Hydrogen released as such is compressed by a pump (P2) where the valve (V2) is in an opened state and supplied to the pressure valve (B2).
  • the hydrogen brought to a predetermined pressure via the said pressure valve (B2) is supplied into the hydrogen fuel tank (4) and is absorbed with the above-mentioned hydrogen storage metal alloy.
  • the above-mentioned controller (3) adjusts the temperature of the said hydrogen storage metal alloy to 40°C or lower so that hydrogen can be repeatedly absorbed and released.
  • the said controller (3) can lower the temperature of the hydrogen storage metal alloy during the hydrogen absorption and elevate the temperature of hydrogen storage metal alloy during the hydrogen release, particularly at the final stage of hydrogen release, whereby an amount of hydrogen suppliable to the fuel battery cell can be increased and much more generation of electric power becomes available.
  • 1 is a fuel battery cell
  • 2 is an inverter
  • 3 is a controller (controlling member)
  • 4 is a hydrogen fuel tank (hydrogen storage tank);
  • 5 is a heat exchanger (temperature adjusting means).

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EP99973803A 1999-03-29 1999-11-24 Legierung zum wasserstoffspeichern, verfahren zum absorbieren und freisetzen von wasserstoff durch den gebrauch der legierung und wasserstoffbrennstoffzelle zur anwendung des verfahrens Ceased EP1176219A4 (de)

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EP1291949A2 (de) * 2001-09-07 2003-03-12 Toyota Jidosha Kabushiki Kaisha Brennstoffzellensystem, Verfahren zu ihrer Steuerung und damit ausgestattes Fahrzeug
EP1464886A2 (de) * 2003-03-31 2004-10-06 Asia Pacific Fuel Cell Technologies, Ltd. Heizvorrichtung für Wasserstoffspeicherbehälter
DE112005002944B4 (de) * 2004-12-24 2010-01-07 Kabushiki Kaisha Toyota Jidoshokki, Kariya Brennstoffzellensystem
EP2759515A4 (de) * 2011-11-08 2015-06-17 Atsumitec Kk Verfahren für wasserstoffeinschluss

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US6835490B1 (en) * 1999-03-29 2004-12-28 Tohoku Techno Arch Co., Ltd. Alloy for hydrogen storage, method for absorption and release of hydrogen using the alloy, and hydrogen fuel cell using the method
CA2362638C (en) * 1999-12-17 2009-12-15 Tohoku Techno Arch Co., Ltd. Hydrogen storage metal alloy and production thereof
JP4944300B2 (ja) * 2001-01-25 2012-05-30 本田技研工業株式会社 燃料電池システム
US7108757B2 (en) * 2003-08-08 2006-09-19 Ovonic Hydrogen Systems Llc Hydrogen storage alloys providing for the reversible storage of hydrogen at low temperatures
CA2529427C (en) * 2004-12-17 2011-03-15 University Of New Brunswick Synthesis, recharging and processing of hydrogen storage materials using supercritical fluids
JP4863651B2 (ja) * 2005-06-09 2012-01-25 本田技研工業株式会社 燃料電池システム
CN100457946C (zh) * 2006-03-01 2009-02-04 四川大学 长循环寿命的钒基固溶体贮氢合金
US20080296904A1 (en) * 2007-05-29 2008-12-04 Nasik Elahi System for capturing energy from a moving fluid
US20130309588A1 (en) * 2012-05-15 2013-11-21 GM Global Technology Operations LLC Integrated cryo-adsorber hydrogen storage system and fuel cell cooling system
JP6060028B2 (ja) * 2013-04-22 2017-01-11 株式会社神戸製鋼所 ガス圧縮機及び摩耗状態判定方法
US20160118654A1 (en) * 2014-10-24 2016-04-28 Ovonic Battery Company, Inc. Bcc metal hydride alloys for electrochemical applications
FR3060552B1 (fr) * 2016-12-20 2022-01-21 Airbus Safran Launchers Sas Systeme de generation de dihydrogene gazeux
KR20200134904A (ko) 2019-05-24 2020-12-02 (주) 고송이엔지 수소연료전지용 셀의 자동 레이아웃 장치에 적용되는 히팅 블럭 및 상기 히팅 블럭을 포함하는 수소연료전지용 셀의 자동 레이아웃 장치
KR20200134903A (ko) 2019-05-24 2020-12-02 (주) 고송이엔지 수소연료전지용 셀의 자동 레이아웃 장치
KR102376878B1 (ko) 2020-05-22 2022-03-21 (주) 고송이엔지 수소연료전지용 셀 제조를 위한 가스 확산층 업로드 장치

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EP1291949A2 (de) * 2001-09-07 2003-03-12 Toyota Jidosha Kabushiki Kaisha Brennstoffzellensystem, Verfahren zu ihrer Steuerung und damit ausgestattes Fahrzeug
EP1291949A3 (de) * 2001-09-07 2008-03-26 Toyota Jidosha Kabushiki Kaisha Brennstoffzellensystem, Verfahren zu ihrer Steuerung und damit ausgestattes Fahrzeug
US7419735B2 (en) 2001-09-07 2008-09-02 Toyota Jidosha Kabushiki Kaisha Fuel cell system, method of controlling the same, and vehicle mounted with the same
EP1464886A2 (de) * 2003-03-31 2004-10-06 Asia Pacific Fuel Cell Technologies, Ltd. Heizvorrichtung für Wasserstoffspeicherbehälter
EP1464886A3 (de) * 2003-03-31 2005-01-12 Asia Pacific Fuel Cell Technologies, Ltd. Heizvorrichtung für Wasserstoffspeicherbehälter
DE112005002944B4 (de) * 2004-12-24 2010-01-07 Kabushiki Kaisha Toyota Jidoshokki, Kariya Brennstoffzellensystem
EP2759515A4 (de) * 2011-11-08 2015-06-17 Atsumitec Kk Verfahren für wasserstoffeinschluss
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